Characterization of surface composition of platinum and ruthenium nanoalloys dispersed on active carbon

Supported samples of 8 wt % monometallic Pt/C and Ru/C, as well as 12 wt % bimetallic Pt50Ru50/C, were prepared by the method of incipient wetness impregnation. Impregnated samples were subsequently reduced by hydrogen and then oxidized in air at different To temperatures. TEM and XRD examinations indicated that metal crystallites were finely dispersed with a diameter of dM < or = 3 nm on the reduced samples. Reductive behavior of the oxidized samples by hydrogen was pursued with the technique of temperature programmed reduction (TPR). The temperature of the reduction peaks (Tr) noticed in the TPR profiles varied with the metal composition of catalysts and To temperature of oxidation. At To = 300 K, oxidation was confined to the surface layer of metallic crystallites. As a result, Pts O (with a peak at Tr = 230 K) or PtsO2 (Tr = 250 K) was formed on monometallic Pt/C while RusO2 (Tr approximately 380 K) was formed on Ru/C. A reductive peak with Tr = 250 K was found from the bimetallic sample from Pt50Ru50/C oxidized at To = 300 K. The reductive peak suggests bimetallic crystallites were dispersed with cherry type structure, with Pt exposed at the surface and Ru in the core. On increasing the To temperature of oxidation treatment to 370 K and higher, Tr peaks between 270 and 350 K were gradually noticed on the oxidized bimetallic sample. Peaks in this Tr region are assigned to reduction of the oxidized alloy surface (AsO). Evidently, a segregation of Ru to the surface of the bimetallic crystallites is indicated upon oxidation at To > 380 K.     

Bimetallic Cluster Provides a Higher Activity Electrocatalyst for Methanol Oxidation

The cluster complex Pt₂Ru₄(CO)₁₈ was used as a precursor to prepare a 60 wt% 1:2 Pt:Ru nanoparticles on carbon (PtRu/C) for use as an electrocatalyst for methanol oxidation. This bimetallic carbonyl cluster complex was found to provide smaller, more uniform bimetallic nanoparticle that exhibited higher electrocatalytic activity than a 60 wt% 1:1 Pt:Ru commercial catalyst from E-Tek. Using bimetallic cluster precursors simplifies the synthetic procedures by reducing the need for high temperature reduction and assures a more intimate mixing of the two different metals. Transmission electron microscopy (TEM) images of the catalyst obtained from the cluster precursor showed bimetallic nanoparticles having a narrow size range of 2–3 nm that were dispersed uniformly over the surface of the support. Images of the commercial catalyst showed particles 3–4 nm in diameter that tended to agglomerate near the edges of the carbon support particles. Cyclic voltammograms of methanol oxidation from the two catalysts showed significantly higher activity for the cluster-derived catalyst. The onset potential for methanol oxidation for the cluster-derived catalyst was approximately 170 mV lower than that of the commercial catalyst at 100 A/g Pt, and approximately 250 mV lower at 400 A/g Pt. ^* This report is dedicated to Prof. Günter Schmid on the occasion of his 70th birthday.     

Pt-Ru合金薄膜的电沉积制备及其电化学表面增强红外吸收光谱

在1mmol·L-1H2PtCl6+1mmol·L-1RuCl3+0.1mol·L-1H2SO4镀液中采用电沉积法在化学镀金膜的红外窗口Si反射面上制备Pt50Ru50合金电极.利用原子力显微镜(AFM)可以观察到制备的Pt50Ru50合金电极形貌呈现出100-200nm大小的颗粒.常规电化学分析方法得出该电极具有典型的合金特征,对CO和CH3OH具有很好的催化氧化作用.应用电化学现场衰减全反射表面增强红外光谱法(ATR-SEIRAS)可以观察到该电极上Pt位和Ru位上CO的振动谱峰,且表现出Pt-Ru二元金属良好的协同催化性能.     

Structures and catalytic properties of PtRu electrocatalysts prepared via the reduced RuO2 nanorods array

Structures and properties of PtRu electrocatalyts, derived from the aligned RuO2 nanorods (RuO2NR), are investigated using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and cyclic voltammetry toward COads and methanol oxidation. The catalytic activity of methanol oxidation and the CO tolerance are promoted significantly by reducing RuO2 into Ru metal before decorating with Pt. Reduction of RuO2NR was carried out by either thermal decomposition at 650 degrees C in vacuum or H2-reduction at 130 degrees C in low-pressure hydrogen. Reduction assisted by hydrogen allows infiltrating decomposition at low temperature and produces an array of nanorods with rugged walls featuring small Ru nuclei and larger surface area. Pt-RuNR, whose surface Pt:Ru ratio=0.58:0.42 was prepared by decorating with 0.1 mg cm(-2) Pt on the H2-reduced array containing 0.39 mg cm(-2) Ru, demonstrates a favorable combination of CO tolerance and high methanol oxidation activity superior to other RuO2NR-derived catalysts. When compared with a commercial electrocatalyst of PtRu (1:1) alloy (<4 nm), the activity of Pt-RuNR in methanol oxidation is shown to be somewhat lower at potential<0.48 V and higher at potential>or=0.48 V.     

Nanostructured PtRu/C as anode catalysts prepared in a pseudomicroemulsion with ionic surfactant for direct methanol fuel cell

Nanostructured PtRu/C catalysts have been prepared from a water-in-oil pseudomicroemulsion with the aqueous phase of a mixed concentrated solution of H(2)PtCl(6), RuCl(3), and carbon powder, oil phase of cyclohexane, ionic surfactant of sodium dodecylbenzene sulfonate (C(18)H(29)NaO(3)S), and cosurfactant n-butanol (C(4)H(10)O). Two different composing PtRu/C nanocatalysts (catalyst 1, Pt 20 wt %, Ru 15 wt %; catalyst 2, Pt 20 wt %, Ru 10 wt %) were synthesized. The catalysts were characterized by transmission electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, and thermogravimetric analysis, and the particles were found to be nanosized (2-4 nm) and inherit the Pt face-centered cubic structure with Pt and Ru mainly in the zero valance oxidation state. The ruthenium oxide and hydrous ruthenium oxide (RuO(x)()H(y)()) were also found in these catalysts. The cyclic voltammograms (CVs) and chronoamperometries for methanol oxidation on these catalysts showed that catalyst 1 with a higher Ru content (15 wt %) has a higher and more durable electrocatalytic activity to methanol oxidation than catalyst 2 with low Ru content (10 wt %). The CV results for catalysts 1 and 2 strongly support the bifunctional mechanism of PtRu/C catalysts for methanol oxidation. The data from direct methanol single cells using these two PtRu/C as anode catalysts show the cell with catalyst 1 has higher open circuit voltage (OCV = 0.75 V) and maximal power density (78 mW/cm(2)) than that with catalyst 2 (OCV = 0.70 V, P(max) = 56 mW/cm(2)) at 80 degrees C.     

直接甲醇燃料电池高稳定性Pt/RuO_2/C阴极催化剂研究

应用湿化学法制备RuO2/C纳米复合物,并以其为载体借助微波法制备成Pt/RuO2/C催化剂.使用透射电镜和X射线衍射分析RuO2/C载体、Pt/RuO2/C催化剂的形貌及晶体结构;循环伏安、稳态阳极腐蚀和旋转圆盘电极等测试电化学性能.结果表明,Pt/RuO2/C催化剂具有良好的耐甲醇渗透性和稳定性,可有效延长催化剂的使用寿命.本文为探索新型高性能DMFC阴极催化剂之制备提供了一条较好的途径.     

Transmission electron microscopy studies of the nanoscale structure and chemistry of Pt50Ru50 electrocatalysts.

The structural and chemical heterogeneity of 2.5-nm Pt50Ru50 electrocatalysts was studied by transmission electron microscopy using selected area diffraction, lattice imaging, electron-energy loss spectroscopy, and energy-dispersive X-ray spectroscopy. The catalysts with the highest methanol oxidation activities exhibit oxidation-induced phase separation on the nanoscale to from Pt-rich metal embedded in Ru-rich hydrous and anhydrous oxide. Reduction of the oxide-on metal samples produces a true bimetallic face-centered cubic Pt50Ru50 alloy, with 275 times lower oxidation activity.     

Electrocatalysts for methanol oxidation with ultra low content of Pt and Ru

We have developed efficient electrocatalysts for methanol oxidation using new synthetic method facilitating deposition of Pt–Ru very thin nanoplatelets on carbon nanoparticles The method involves oxidation of carbon support, adsorption of Pb²⁺, its reduction and galvanic displacement of Pb⁰ by Pt and/or Ru. The Pt mass activity of this catalyst is about 10 times higher than that of the commercial Pt–Ru/C. The catalyst with the 1:1 Pt/Ru ratio displayed the highest methanol oxidation activity per surface Pt atom. Our results demonstrate the new synthetic method that yields the catalyst with potential for solving the problem of high Pt loading in direct methanol fuel cell anodes.     

Ru(0001) model catalyst under oxidizing and reducing reaction conditions: in-situ high-pressure surface X-ray diffraction study

With surface X-ray diffraction (SXRD) using a high-pressure reaction chamber we investigated in-situ the oxidation of the Ru(0001) model catalyst under various reaction conditions, starting from a strongly oxidizing environment to reaction conditions typical for CO oxidation. With a mixture of O(2) and CO (stoichiometry, 2:1) the partial pressure of oxygen has to be increased to 20 mbar to form the catalytically active RuO(2)(110) oxide film, while in pure oxygen environment a pressure of 10(-5) mbar is already sufficient to oxidize the Ru(0001) surface. For preparation temperatures in the range of 550-630 K a self-limiting RuO(2)(110) film is produced with a thickness of 1.6 nm. The RuO(2)(110) film grows self-acceleratedly after an induction period. The RuO(2) films on Ru(0001) can readily be reduced by H(2) and CO exposures at 415 K, without an induction period.     

Pt/RuO2/CNTs纳米催化剂中RuO2含量对甲醇电催化氧化性能的影响

制备了一种新的甲醇直接燃料电池Pt/RuO2/CNTs阳极催化剂,在相同Pt负载量下,其甲醇电催化氧化活性是Pt/CNTs的3倍.采用循环伏安法研究发现Pt/RuO2/CNTs纳米催化剂中RuO2含量对甲醇电催化氧化活性有明显影响,当Pt和RuO2在碳纳米管上含量分别为15%和9.5%时,Pt/RuO2/CNTs催化剂具有最佳的甲醇电催化氧化活性.RuO2负载在碳纳米管上比电容的变化,反映了水合RuO2结构中质子与电子传输平衡的能力,分析表明,催化剂中RuO2含量不同导致电容的变化是影响甲醇电催化氧化活性的主要原因.当催化剂结构中质子与电子传输达到平衡时,催化剂比电容最大,电催化氧化活性最高.这种基于电容关联电催化剂的观点对甲醇直接燃料电池阳极催化剂的设计非常有意义.     

Cr对Pt-Sn /γ-Al2O3催化剂丙烷脱氢性能的影响

通过H2-TPR、O2-脉冲等表征手段，结合丙烷脱氢催化性能考察了助剂Cr对Pt-Sn/γ-Al2O3催化剂反应性能的影响。结果表明，添加少量Cr可显著改善Pt-Sn/γ-Al2O3催化剂的脱氢稳定性，可提高丙烯选择性，降低催化剂表面积炭量。这是由Cr和Pt-Sn之间存在的协同作用引起的，一方面，Pt促进了Cr的还原，生成了可提高丙烯选择性的+3价Cr；另一方面，Cr使Sn变得难于还原，在强还原气氛下保持了活性氧化态价态，进而改善了催化剂的脱氢稳定性。     

Novel method for the synthesis of hydrophobic Pt-Ru nanoparticles and its application to preparing a Nafion-free anode for the direct methanol fuel cell

Pt-Ru alloy is a bimetallic catalyst most commonly used in the direct methanol fuel cell (DMFC). In this paper, a new process to synthesize an unsupported Pt-Ru colloid has been introduced. The characteristics of synthesized nanoparticles were identified by XRD, TEM/EDX, and SEM, and it shows that Ru atoms are incorporated into the Pt fcc structure and the well-dispersed particles (diameter approximately 4 nm) possess a Pt-rich feature. This catalyst shows a hydrophobic characteristic which can adsorb very well on the hydrophobic-treated carbon paper or carbon cloth without the need of Nafion. Accordingly, this method can avoid particle agglomeration, and the synthesized catalyst demonstrates strong adsorption with carbon paper. In addition, this colloid-type Nafion-free catalyst was measured via linear sweep voltammetry (LSV) and exhibited electrochemical activity for methanol oxidation comparable to the commercial one with Nafion binding.     

In situ time-resolved XAFS study on the structural transformation and phase separation of Pt3Sn and PtSn alloy nanoparticles on carbon in the oxidation process

The dynamic behavior and kinetics of the structural transformation of supported bimetallic nanoparticle catalysts with synergistic functions in the oxidation process are fundamental issues to understand their unique catalytic properties as well as to regulate the catalytic capability of alloy nanoparticles. The phase separation and structural transformation of Pt(3)Sn/C and PtSn/C catalysts during the oxidation process were characterized by in situ time-resolved energy-dispersive XAFS (DXAFS) and quick XAFS (QXAFS) techniques, which are element-selective spectroscopies, at the Pt L(III)-edge and the Sn K-edge. The time-resolved XAFS techniques provided the kinetics of the change in structures and oxidation states of the bimetallic nanoparticles on carbon surfaces. The kinetic parameters and mechanisms for the oxidation of the Pt(3)Sn/C and PtSn/C catalysts were determined by time-resolved XAFS techniques. The oxidation of Pt to PtO in Pt(3)Sn/C proceeded via two successive processes, while the oxidation of Sn to SnO(2) in Pt(3)Sn/C proceeded as a one step process. The rate constant for the fast Pt oxidation, which was completed in 3 s at 573 K, was the same as that for the Sn oxidation, and the following slow Pt oxidation rate was one fifth of that for the first Pt oxidation process. The rate constant and activation energy for the Sn oxidation in PtSn/C were similar to those for the Sn oxidation in Pt(3)Sn/C. In the PtSn/C, however, it was hard for Pt oxidation to PtO to proceed at 573 K, where Pt oxidation was strongly affected by the quantity of Sn in the alloy nanoparticles due to swift segregation of SnO(2) nanoparticles/layers on the Pt nanoparticles. The mechanisms for the phase separation and structure transformation in the Pt(3)Sn/C and PtSn/C catalysts are also discussed on the basis of the structural kinetics of the catalysts themselves determined by the in situ time-resolved DXAFS and QXAFS.     

A new supported catalyst for methanol oxidation prepared by a reverse micelles method

Carbon supported platinum–ruthenium alloy catalyst prepared by reverse micelles method for was proposed. The particle size and morphology of catalyst were determined by XRD and TEM and found to be homogeneously dispersed on carbon support with narrow particle size distribution. The performance of the Pt–Ru/C catalyst was tested by cyclic voltammogram and galvanostatic polarization experiments in 1 M sulfuric acid with 2 M methanol solution at room temperature and showed a higher catalytic activity when compared with the standard Pt–Ru/C (E-TEK) catalyst.     

Cooperation between Pt and Ru on RuPt/AC bimetallic catalyst in the hydrogenation of phthalates

RuPt/AC bimetallic catalysts were pre pared by two-step incipient impregnation method and evaluated in the hydrogenation of phthalates.According to the characterization results,well dispersed Ru Pt bimetallic nanoparticles were formed on the catalyst,and the strong interaction between the two metals resulted in the formation of RuPt alloy.It was found that Ru can donate electrons to Pt on RuPt alloy nanoparticles,leading to the formation of electron-deficient Ru which significantly promotes the hydrogenation rate of dioctyl phthalate and improves the selectivity of dioctyl di-2-ethylhexylcyclohexane-1,4-dicarboxylate by accelerating the further hydrogenation of intermediate products.The bimetallic RuPt catalyst also presented excellent stability and versatility in the hydrogenation of phthalates,demonstrating its prospective future in the hydrogenation of aromatic ring contained compounds.     

In-situ X-ray absorption spectroscopy study of Pt and Ru chemistry during methanol electrooxidation

Methanol electrooxidation in a 0.5 M sulfuric acid electrolyte containing 1.0 M CH3OH was studied on 30% Pt/carbon and 30% PtRu/carbon (Pt/Ru = 1:1) catalysts using X-ray absorption spectroscopy (XAS). Absorption by Pt and Ru was measured at constant photon energy in the near edge region during linear potential sweeps of 10-50 mV/s between 0.01 and 1.36 V vs rhe. The absorption results were used to follow Pt and Ru oxidation and reduction under transient conditions as well as to monitor Ru dissolution. Both catalysts exhibited higher activity for methanol oxidation at high potential following multiple potential cycles. Correlation of XAS data with the potential sweeps indicates that Pt catalysts lose activity at high potentials due to Pt oxidation. The addition of Ru to Pt accelerates the rate of methanol oxidation at all potentials. Ru is more readily oxidized than Pt, but unlike Pt, its oxidation does not result in a decrease in catalytic activity. PtRu/carbon catalysts underwent significant changes during potential cycling due to Ru loss. Similar current density vs potential results were obtained using the same PtRu/carbon catalyst at the same loading in a membrane electrode assembly half cell with only a Nafion (DuPont) solid electrolyte. The results are interpreted in terms of a bifunctional catalyst mechanism in which Pt surface sites serve to chemisorb and dissociate methanol to protons and carbon monoxide, while Ru surface sites activate water and accelerate the oxidation of the chemisorbed CO intermediate. PtRu/carbon catalysts maintain their activity at very high potentials, which is attributed to the ability of the added Ru to keep Pt present in a reduced state, a necessary requirement for methanol chemisorption and dissociation.     

Electrocatalytic oxidation of methanol on Pt-Pd nanoparticles supported on honeycomb-like porous carbons in alkaline media

Honeycomb-like porous carbons (PCs) were synthesized using a facile self-assembly method with phenolic resin as the carbon source and tetraethyl orthosilicate (TEOS) as the silica source. The PCs were found to have a large BET surface area of 458 m² g^?1 and a partially graphitized structure. The obtained PCs were used as a support for various Pt-Pd bimetallic alloy catalysts employed for methanol oxidation in alkaline media. Compared with Pt supported on commercial Vulcan XC-72R carbon (Pt/C) and with the other Pt-Pd bimetallic alloy catalysts on PCs, Pt₃Pd₁ on PCs displayed the most negative onset potential for methanol oxidation and the highest steady-state current (2.04 mA cm^?2). This may be because the Pt₃Pd₁/PCs catalyst has the largest electrochemical active surface area (ESA), and because adding Pd to the catalyst improves the ability of the intermediate species to tolerate oxidation. The results show that the prepared Pt-Pd/PCs is a potential candidate for application as a catalyst in alkaline direct methanol fuel cells.     

Physical and electrochemical characterizations of microwave-assisted polyol preparation of carbon-supported PtRu nanoparticles

PtRu nanoparticles supported on Vulcan XC-72 carbon and carbon nanotubes were prepared by a microwave-assisted polyol process. The catalysts were characterized by transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). The PtRu nanoparticles, which were uniformly dispersed on carbon, were 2-6 nm in diameter. All PtRu/C catalysts prepared as such displayed the characteristic diffraction peaks of a Pt face-centered cubic structure, excepting that the 2theta values were shifted to slightly higher values. XPS analysis revealed that the catalysts contained mostly Pt(0) and Ru(0), with traces of Pt(II), Pt(IV), and Ru(IV). The electro-oxidation of methanol was studied by cyclic voltammetry, linear sweep voltammetry, and chronoamperometry. It was found that both PtRu/C catalysts had high and more durable electrocatalytic activities for methanol oxidation than a comparative Pt/C catalyst. Preliminary data from a direct methanol fuel cell single stack test cell using the Vulcan-carbon-supported PtRu alloy as the anode catalyst showed high power density.     

PtRu nanoparticle electrocatalyst with bulk alloy properties prepared through a sonochemical method

Properties of PtRu nanoparticles prepared using high-intensity sonochemistry are reported. Syntheses were carried out in tetrahydrofuran (THF) containing Ru3+ and Pt4+ in a fixed mole ratio of either 1:10 or 1:1. X-ray diffraction measurements confirmed sonocation produces an alloy phase and showed that the composition of the nanometer scale metal particles is close to the mole fraction of Ru3+ and Pt4+ in solution with deviations that tend toward Ru enrichment in the alloy phase. The materials gave responses that are similar in terms of peak potential and current density, referenced to the catalyst active surface area, to those of bulk alloys in voltammetry experiments involving CO stripping and CH3OH electrochemical oxidation in 0.1 M H2SO4. The results show that sonochemical methods have the potential to produce nanometer scale bimetallic electrocatalysts that possess alloy properties. The materials have application in mechanistic studies of fuel cell reactions and as platforms for the development of CO tolerant fuel cell catalyst.     

Structural analysis of sonochemically prepared PtRu versus Johnson Matthey PtRu in operating direct methanol fuel cells

Sonochemically prepared PtRu (3 : 1) and Johnson Matthey PtRu (1 : 1) were analyzed by X-ray absorption spectroscopy in operating liquid feed direct methanol fuel cells. The total metal loadings were 4 mg cm(-2) unsupported catalysts at the anode and cathode of the membrane electrode assembly. Ex situ XRD lattice parameter analysis indicates partial segregation of the Ru from the PtRu fcc alloy in both catalysts. A comparison of the in situ DMFC EXAFS to that of the as-received catalyst shows that catalyst restructuring during DMFC operation increases the total metal coordination numbers. A combined analysis of XRD determined grain sizes and lattice parameters, ex situ and in situ EXAFS analysis, and XRF of the as-received catalysts enables determination of the catalyst shell composition. The multi-spectrum analysis shows that the core size increases during DMFC operation by reduction of Pt oxides and incorporation of Pt into the core. This increases the mole fraction of Ru in the catalyst shell structure.